Amine salts of 2,2&#39;-thiobis



United States PatentQ I AMINE SALTS on 2,2'-THIOBIS (4,6-DICHLOROPHENYL) Milton Kosmin, Dayton, Ohio, .assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing." Application March 20, 1956 Serial No. 572,626

3 Claims, romeo-561.5

OIELX. OH.X

in which X is a salt-forming N-alkenylpolyalkylenepolyamine having from 8 to .18 carbon atoms in the alkenyl radical, from 2 to 4 amino groups in the molecule, from 2 to 3 carbon atoms in the alkylene chain and from 1 to 3 alkylene groups in the molecule'and m is aninteger of to 1.

The new salts are prepared by treating a 2,2-thiobis- (dichlorophenol) with a suitable alkenylpolyalkylenepolyamine. Examples of thiophenols useful for the present purpose are 2,2-thiobis(4,6-dichlorophenol), 2,2'-thiobis- (5,6 dichlorophenol) and 2,2 thiobis(3,5 dicialorophenol). The thiobis(dichlorophenols) are readily obtainable, known compounds which may be prepared by reaction of sulfur monochloride or dichloride with the appropriate dichlorophenol or by nuclear chlorination of thiobisphenol to give dichlorination in each of the benzene nuclei.

As examples of 2,2'-thiobis(dichlorophenol) salts provided by the present invention may he mentioned the following:

N-octenylpropylenediamine salt of 2,2'-thiobis(3,5-dichlorophenol) N-decenyldiethylenetriamine salt of 2,2'-thiobis(4,6-di-,

chlorophenol) Bis (N-dodecenyltriethylenetetramine) salt of 2,2'-thiobis- (5,6-dichlorophenol) N-hexadecenyldiethylenetriamine salt of 2,2'-thiobis(3,4-

dichlorophenol) Bis(N-octadecenylethylenediamine) salt of 2,2'-thiobis- (4,5-dichlorophenol) N-tetradecenyltriethylenediamine salt of 2,2'-thiobis(4,6-

dichlorophenol) 2,897,235 Patented July 28 1959 P we 2' found, moreover, that not only the water-solubility pro erties of the thiobis(dichlorophenols) are improved by converting them into the amine salts, but that the salts demonstrate .a marked affinity for textile fibers, particularly for fibers of .cellulosic origin. The present salts are'selectively absorbed by cellulosic fibers from water solutions or emulsions thereof, and are retained on said fibers for long periods of time, even after numerous washingsf They thus function not only as biocidally active materials, but also as rewetting agents, 'i.e., textile fabrics are easily wetted when immersed into a bath containing the amine salt; 'and since the salt is retained on the fibers, fabrics which have been treated therewith .are subsequently easily wetted by water containing no wetting-out agent. This substantive effect of the present amine salts is particularly valuable when the fibers ortextiles are to be submitted to subsequent treatments, e.g., to bleaching, washing, rinsing, or dyeing operations.

7 Conversion of the 2,2'-thiobis(dichlorophenols) to the present amine salts is effected by simply adding the amine to the phenol in the presence ofan inertdiluent and allowadvantageously employed.

Because neutralization of the phenol with some of the amines involves some degree of heat-evolution, it is generally expedient to mix the two reactants gradually.

Usually, when dropwise addition of, say the amine, is

employed, neutralization of the phenol is complete when the"stoichiometric'quantity of amine has been added.

For convenience in isolating the product, it is generally advantageous to effect the reaction in a medium which is a solvent for the phenol, but a non-solvent for the salt product. Generally useful inert diluents or solvents, however, are paraffinic or aromatic hydrocarbons such as hexane, kerosene, benzene or toluene; chloroor nitroderivatives thereof such as carbon tetrachloride, ethylene dichloride, Z-nitropropane, dichlorobenzene or nitrobenzene; fatty alcohols such as ethanol or isobutanol, ethers such as ethyl ether or dioxane, etc.

The invention is further illustrated, but not limited, by the following example:

Example This example shows preparation of an N-dodecenyldiethyIene triamine salt of 2,2'-thiobis(4,6-dich1orophenol). The N-dodecenyldiethylenetriamine was obtained by the addition reaction of diethylenetriamine with the reaction product of propylene tetramer and hypochlorous acid and will be hereinafter referred to as N-(tetrapropenyl)diethylenetriamine, this nomenclature being believed to denote properly the branched structure of the dodecenyl radical as well as its origin.

The phenol (35.5 g., 0.1 mole) was dispersed in 200 ml. of ethanol, and there was then gradually added to the dispersion 28.0 g. (0.1 mole) of the N-(tetrapropenyl)diethylenetriamine. Some heat was evolved. The mixture was then allowed to cool and then submitted to distillation under partial pressure in order to remove the ethanol. The residue was dried in a vacuum oven to give a yellow glassy mass which was readily ground. up to give powder-like crystals of the N-(tetrapropenyl)diethylenetriamine salt of 2,2'-thiobis(4,6-dichlorophenol).

In vitro tests conducted with this salt against the bacilli M icrococcus pyogenes var. aureus and Salmonella typhosa (Hopkins strain) disclosed no growth of these organisms at a 1:5 million dilution, thus showing that the bacteriostatic activity of the free phenol was not impaired by converting it to the amine salt, although the parent phenol represented only a portion of the total weight of the salt. Treatment of a cotton fabric with an aqueous solution of the salt'and subsequent immersion of the dried, treated cloth into hard water showed the cloth to be very easily wetted. 7 w 1 The present amine salt need not, however, be first isolated before being applied to textiles. Aqueous solutions of the thiobisphenol amine salt may be prepared by separately dissolving the thiobisphenol and the desired amine in Water in suflicient amount to form a textile treating bath. By reason of the amine-induced sub-;

stantivity of the thiobisphenol, treating baths may contain from 0.01% to 1% or more of the salt-forming ingredients. Cellulose-containing textiles treated in such baths will acquire and retain a high degree of resistance to fungus and bacterial organisms.

Moreover, by reason of the substantivity of-the present compositions, they are particularly effective when employed in the process of washing textiles with soaps or with synthetic detergents of all types. Soaps or synthetic detergent compositions may be prepared containing the present amine salt either in the form of soap or detergent aqueous washing solutions or in the dry -form, for example, in bar or powdered detergent form. Soaps: suitable for the present purpose are the conventional fatty acid soaps, While the detergents may be either nonionic or anionic washing materials. ionic detergents comprise the alkaline oxide, particularly ethylene oxide condensation products of fatty acid alco-, hols or acids having more than 8 carbon atoms in the molecule. Well-known anionic detergents comprise the Conventional nonalkali metal or amine salts of sulfonated alkylated aro- This is a continuation-in-part of my co-pending appliin which X is a salt-forming N-alkenylpolyalkylenepolyamine having from 8 to 1 8,carbon atoms in the alkenyl radical, from 2 I04 amino groups in the molecule, from 2 to 3 carbons atoms in the'alkylene chain and from 1 to 3 alkylene groups in the molecule and m is an integer of 0 to 1.

2. A salt of' 2,2'-thiobis(4,6-dichlorophenol) and, an N-alkenylpolyalkylenepolyamine having from 8 to 18 carbon atoms in the alkenyl radical, from 2 to 4 amino groups in the molecule, from 2 to 3 carbon atoms in the alkylene chain and from 1 to 3 alkylene groups in the molecule.

3. A salt of 2,2'-tl1iobis(4,6-dichlorophenol) and an N-dodecenyldiethylenetriamine wherein the N-dodecenyl radical has a branched chain structure.

References Cited in the file of this patent UNITED STATES PATENTS 2,353,735 Kunz et al. July 18, 1944 2,362,464 Britton et' a1. Nov. 14, 1944 2,630,458 Moyle et al Mar. 3, 1953 2,695,317 Cutler Nov. 23, 1954 2,702,302 Cook et al. Feb. 15, 1954 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0o 2,897,235 July 28, 1959 Milton Kosmin It is hereby certified that error appears in the above numbered patent requiring correction and that Patent should read as correctedbelown 'In the heading to the printed specification line 3 title of invention, for that portion reading (4,6-DICHLOROPHENYL)" read (4,6-DICHLOROPHENOL) Signed and sealed this 16th day of August 1960c (SEAL) Attest:

KARL H AXLINE 7 ROBERT C. WATSON Attesting Officer 'Conmissioner of Patents the said Letters 

1. A SALT HAVING THE FORMULA 